Metal catalyzed reactions

ABSTRACT

Compositions and processes of forming chemical bonds, such as carbon-carbon and carbon-heteroatom bonds are provided. The compositions include at least one α-halo carbonyl compound, and one or more transmetallation reagents. The transmetallation reagents are formed by the addition of a metal or metal catalyst to a target compound. The target compound is the compound undergoing chemical bond formation. Bond formation can be carried out in both intermolecular reactions (i.e. between two or more target compounds), or intramolecular (within the same target compound) reactions.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority from U.S. provisional patentapplication Serial No. 60/280,275 filed Mar. 30, 2001 entitledTransition Metal Catalyzed Reactions, the entire disclosure of which isincorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to a composition and process offorming chemical bonds, such as carbon-carbon and carbon-heteroatombonds. The present invention has particular applicability to theformation of chemical bonds by transmetallation reaction chemistry.

BACKGROUND

[0003] Over the past several decades, palladium (Pd) catalyzedcarbon-carbon bond formation reactions have been extensively studied andwidely applied in organic synthesis [Tsuji, J. Transition Metal Reagentsand Catalysis, John Wiley: Chichester, 2000]. The ultimately formedchemical bonds are produced by a sequence of intermediates. Theseinclude the formation of an aryl or alkenylpalladium halide complexgenerated by oxidative addition of the aryl or alkenylhalide with Pd.These complexes can, in turn, undergo transmetallation with manyreagents. This reaction sequence is followed by reductive elimination toform a carbon-carbon bond and to regenerate a Pd (0) species. Thissystem provide a methods for developing many crosscoupling reactions.The following authors are known to employ the element in theparentheticals for coupling reactions: Suzuki (boron, B), Stille (tin,Sn), Negeshi (zinc and aluminum, Zn and Al), Kumada (magnesium, Mg)[Miyaura, N.; Suzuki. A. Chem. Rev. 1995, 95, 2457; Knight, D. W. InComprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Ed.;Pergamon Press: Oxford, 1991, Vol 3, Chapter 2.3; Suzuki, A. Pure Appl.Chem. 1985, 57, 1749; Tamao, K.; Kumada, M. in The Chemistry of theMetal-Carbon Bond (Ed., F. R. Hartley), Vol. 4, Wiley, N.Y., 1987,Chapter 9 p 819; Suzuki, A. Pure Appl. Chem. 1985, 57, 1749; Stille, J.K. Angew Chem. Int. Ed. Engl. 1986, 25, 508; Negishi, E. Acc. Chem. Res.1982, 15, 340. (i) Kumada, M. Pure Appl. Chem. 1980, 52, 669].

[0004] In contrast, palladium-catalyzed homocoupling reactions have notbeen studied extensively, although some homocoupling reactions of aryland alkenyl halides facilitated by a Pd species are known. [See, e.g.,Hennings, D. D.; Iwama, T.; Rawal, V. H. Org. Lett. 1999, 1, 1205;Hassan, J.; Penalva, V.; Lavenot, L.; Gozzi, C.; Lemaire, M. Tetrahedron1998, 54, 13793; Jutand, A.; Mosleh, A. J. Org. Chem. 1997, 62, 261;Smith, K. A.; Campi, E. M.; Jackson, W. R.; Marcuccio, S.; Naeslund, C.G. M.; Deacon, G. B. Synlett, 1997, 131; Jutand, A.; Mosleh, A. Synlett,1993, 568; Jutand, A.; Negri, S.; Mosleh, A. Chem. Commun., 1992, 1792;Miura, M.; Hashimnoto, H.; Itoh, K.; Nomura, M. Chem. Lett. 1990, 459].Other known coupling reactions include Glazer coupling (Chem Ber 1869,2, 422, Cadiot P, Chodkiewwicz, W. Chemistry of Acetylenes, 1969, MarcelDekker, New York, p 597), Ullman-type Coupling reactions (Semmelhack, M.F.; Helwuist, P. M.; Jones, L. D. J. Am. Chem. Soc. 1971, 93 5908;Kende, A.; Liebeskind, L. S. Braitsch, D. M. Tetrahdedron Lett. 1975,3375; Prerce, V.; Bae, J. Y.; Zhao, M.; Hill, D. H. J. Org. Chem. 1994,60, 176). For forming carbon-heteroatom bonds, Hartwig and Buchwald havemade a couple of catalysts. Hartwig, J. F. Angew Chem. Int. Ed. Engl.1998, 37, 2047; Wolfe, J. P.; Wagaw, S.; Buchwald, S. L. J. Am. Chem.Soc. 1996, 118, 1133; Mann, G.; Hartwig, J. F. J. Org. Chem. 1997, 62,5413).

[0005] The following table summarizes coupling reactions.

[0006] Although the above mentioned metal-catalyzed andmetal-facilitated carbon-carbon and carbon-heteroatom bond formationreactions are useful for organic synthesis, they are also limited. Forexample, an Ullman coupling reaction generally is carried out underharsh conditions and many hindered or aryl halides having one or moreelectron donating groups resist coupling. Glaser coupling requires thepresence of oxygen, which can destroy many sensitive products,particularly diynes. A number of alkynes with functional groups do notundergo coupling in a Glaser coupling reaction. Moreover, the couplingreaction is generally not applicable to polymerization oroligomerization reactions.

[0007] The synthesis of diynes is particularly problematic as diynes arenot stable and prone to decomposition. Therefore, only alkyl halides,aryl halides (e.g., RI or RBr) that react under mild conditions willcouple. In Sonogashira, Suzuki, Stille, Negishi, Kumada,Hartwig-Buchwald coupling reactions, oxidative addition of aryl halidescan be a difficult step. This is particularly true if the aryl halidehas two groups substituted in adjacent positions. To minimize or avoidthe oxidative addition of these difficult substrates would be of greatinterest in organic synthesis. For a Suzuki coupling reaction, a knownside reaction product is dehalogenation reaction. In Sonogashira,Suzuki, Stille, Negishi, Kumada, Hartwig-Buchwald coupling reactions,the oxidative addition of RX when R is a simple alkyl group with aβ-hydrogen is a slow process and metal compounds can easily formundesirable β-hydrogen elimination products. This has been a majorlimitation of these coupling reactions.

[0008] Hence, there is a need for metal-catalyzed catalytic reactionswhich can improve coupling reactions, or, ideally, overcome many of thelimitation of prior art processes. There is also a need in the chemicalindustry for making existing pharmaceutical products, agrochemicalproducts, polymers products and as well as new products by a facilechemical bond forming reaction.

SUMMARY OF THE INVENTION

[0009] An advantage of the present invention is a composition forchemical bond formation.

[0010] An additional advantage of the present invention is a method offorming chemical bonds by transmetallation.

[0011] Additional advantages, and other features of the presentinvention will be set forth in the description which follows and in partwill become apparent to those having ordinary skill in the art uponexamination of the following or may be learned from the practice of thepresent disclosure. The advantages may be realized and obtained asparticularly pointed out in the appended claims.

[0012] According to the present invention, the foregoing and otheradvantages are achieved in part by a composition comprising at least oneα-halo carbonyl compound; and one or more transmetallation reagents.

[0013] Embodiments include, compositions having a base, e.g. a compoundhaving an available pair of electrons. The forgoing bases includetriethyl amine (Et₃N), DABCO, Et₂NH, NaOR^(b), Na₂CO₃, KF, K₃PO₄, NaOAc,KOH, and R^(b)NX, where R^(b) is one or more of an H, alkyl groups and Xis an anion, such as a halogen or ester. The composition includes atleast one transmetallation reagent. This reagent can be prepare prior toforming the composition or in situ.

[0014] Transmetallation reagents are formed by the addition of a metalor metal catalyst to a target compound. The target compound is thecompound undergoing chemical bond formation. For example,transmetallation reagents include metal complexes, such as RM, RB(OH)₂,RBR′₂, RSnR′₃, RZnX, RHgX, RMgR, RSiR′₃, RCu, ROM, RNHM, RAlR′2, whereinR and R′ are independently an aryl or alkyl group and M is a metal.Other organometallic species are also contemplated. Additionally, anα-halo carbonyl species which can easily undergo oxidative addition withredox active metals is included in this composition for couplingreactions.

[0015] Another aspect of the present invention is forming chemicalbonds. Bond formation can advantageously be carried out in bothintermolecular reactions (i.e. between two or more target compounds), orintramolecular (within the same target compound) reactions. Chemicalbond formation methods can be used to make biologically active compoundsor polymers, such as SP-carbon type of molecules. The method comprisescombining at least one transmetallation reagent comprising a targetcompound with at least one α-halo carbonyl compound; and forming a bondto or within the target compound of the transmetallation reagent.

[0016] In another aspect of the invention, a process for hydroborationand asymmetric hydroboration of boric compounds and coupling ofbisboronic compounds by either intramolecular or intermolecular couplingis contemplated. The process comprises: combining at least one aX-halocarbonyl compound with at least one transmetallation reagent comprisinga boric compound; and coupling the boric compound.

[0017] Additional advantages of the present invention will becomereadily apparent to those skilled in this art from the followingdetailed description, wherein only the preferred embodiments of thepresent invention are shown and described, simply by way of illustrationbut not limitation. As will be realized, the invention is capable ofother and different embodiments, and its several details are capable ofmodification in various obvious respects, all without departing from thespirit of the present invention. Accordingly, the drawings anddescription are to be regarded as illustrative in nature, and not asrestrictive.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates to a composition and process offorming chemical bonds, such as carbon-carbon and carbon-heteroatombonds. The present invention has particular applicability to theformation of chemical bonds by transmetallation reaction chemistry.

[0019] In an embodiment of practicing the present invention, at leastone α-halo carbonyl compound, e.g. an α-bromo carbonyl compound, iscombined with at least one transmetallation reagent comprising a targetcompound; and forming a chemical bond to or within the target compound.Bond formation can advantageously be carried out in both intermolecularreactions (i.e. between two or more target compounds, such as incoupling reactions), or intramolecular (i.e. within the same targetcompound, such as an oxidation reaction) reactions.

[0020] In one aspect of the practicing the method a base is alsocombined with the transmetallation reagent and a-halo carbonyl compound.Useful bases in transmetallation chemistry are known and includetriethyl amine (Et₃N), DABCO, Et₂NH, NaOR^(b), Na₂CO₃, KF, K₃PO₄, NaOAc,KOH, and R^(b)NX, where R^(b) is one or more of an H, alkyl groups and Xis an anion, such as a halogen or ester.

[0021] It is contemplated that the transmetallation reagent can beprepare prior to the intended bond forming reaction or in situ. Thetransmetallation reagents can be formed by the addition of a metal ormetal catalyst to a target compound. The target compound is the compoundundergoing chemical bond formation. The transmetallation reagent caninclude one or more elements consisting of B, Sn, Al, Zn, Mg, Zr, Cu,Hg, and Si or organometalic species. For example, transmetallationreagents include metal complexes, such as RM, RB(OH)₂, RBR′₂, RSnR′₃,RZnX, RHgX, RMgR, RSiR′₃, RCu, ROM, RNHM, RAlR′2, where R and R′ are thetarget compounds and wherein R and R′ are independently an aryl or alkylgroup and M is a metal. Other organometallic species are alsocontemplated. Additionally, an α-halo carbonyl species which can easilyundergo oxidative addition with redox active metals is included in thiscomposition for coupling reactions.

[0022] The transmetallation reagents can be formed by adding a targetcompound to a catalyst or catalyst complex. These are known in the artand include transition metal catalysts, such as Pd(0), Ni(0), Rh(I),Pt(0), Ir(0), Cu(I), Mo(0), Mo(II), and Ru(II) catalysts with or withoutligands as known in the art.

[0023] The catalyst can be selected from the group consisting of PtCl₂;H₂PtCl₄; Pd₂(DBA)₃; Pd(OAc)₂; PdCl₂(RCN)₂; PdCl₂(diphosphine);[Pd(allyl)Cl]₂; Pd(PR₃)₄; [Rh(NBD)₂]X; [Rh (NBD)Cl]₂; [Rh(COD)Cl]₂;[Rh(COD)₂]X; Rh(acac)(CO)₂; Rh(ethylene)₂(acac); [Rh(ethylene)₂Cl]₂;RhCl(PPh₃)₃; Rh(CO)₂Cl₂; RuHX(L)₂; RuX₂(L)₂; Ru(arene)X₂(diphosphine);Ru(aryl group)X₂; Ru(RCOO)₂(diphosphine); Ru(methallyl)2(diphosphine);Ru(aryl group)X₂(PPh₃)₃; Ru(COD)(COT); Ru(COD)(COT)X; RuX₂(cymen);Ru(COD)_(n); Ru(aryl group)X₂(diphosphine); RuCl₂(COD); (Ru(COD)₂)X;RuX₂(diphosphine); RuCl₂(═CHR)(PR′₃)₂; Ru(ArH)Cl₂; Ru(COD)(methallyl)₂;(Ir (NBD)₂Cl)₂; (Ir(NBD)₂)X; (Ir(COD)₂Cl)₂; (Ir(COD)₂)X; CuX (NCCH₃)₄;Cu(OTf); Cu(OTf)₂; Cu(Ar)X; CuX; Ni(acac)₂; NiX₂; (Ni(allyl)X)₂;Ni(COD)₂; NiCl₂(diphosphine); MoO₂(acac)₂; wherein each R and R′ isindependently selected from the group consisting of: alkyl or aryl; Aris an aryl group; and X is a counteranion such as I, Br, Cl, OTf, BF₄,SbF₆, BAr₄; and L represents a ligand.

[0024] Diphosphine include dppe, dppp, dppb, dppf, rac-Binap, chiralbisphosphines, DuPhos, BINAP, BPPM, DIPAMP, DIOP, MCCPM, BCPM, BICP,PennPhos, BPE, ChiraPhos, NorPhos, Degphos, BPPFA, JosiPhos, TRAP,TolBINAP, H8-BINAP, BINAPO, MOP, BINAPHOS, BIPHEMP, SEGPHOS, TUNAPHOS,KetalPhos, f-KetalPhos, HydroPhos, f-HydroPhos, Binaphane, f-Binaphane,FAP; and the mono phosphine includes: PPh₃, P(o-tolyl)₃,tri(2,6-dimethylphenyl)phosphine, P^(t)Bu₃, PCy₃, P(2-Furyl)₃ andPPh₂(o-ArC₆H₄).

[0025] In practicing an embodiment of the invention a transmetallationreagent is combined with at least one ax-halo carbonyl compound. Througha metal-enolate intermediate, the same or different transmetallationreagents can be transferred to a metal center and reductive eliminationgives the desired product. These reactions can advantageously be carriedout to form both intermolecular and/or intramolecular bonds. The methodcan be used to make biologically active compounds or polymers, such asSP-carbon type formation of molecules. An example of a metal mediatedcrosscoupling reaction is provided below.

[0026] Double transmetallation through metal-enolates is alsocontemplated as an aspect of the present invention. In one aspect, thepresent invention relates to transition metal complexes with phosphineligands as catalysts and an α-halocarbonyl compound as a reagent foroxidative addition. The transmetallation reagents can be (R—M) where Ris an alkyl or aryl group, M contains B, Al, Sn, Zn, Mg, Si, Li, Cu, Hg,Zr, with or without other elements. Sometimes, substrates for the ligandexchanging reaction are ROH, RNH₂, RN(R′)H, RSH, CN and R₂P(O)H. Thetransition metal complexes are useful as catalysts in homocouplingreaction, intramolecular cross-coupling reactions and othertransformations.

[0027] Scheme 1 illustrates possible mechanisms of a Pd-catalyzedcrosscoupling and homocoupling reactions. In the palladium-catalyzedcrosscoupling reaction, the reaction is initiated by oxidative additionof R¹—X to Pd, followed by transmetallation of R²—M, and reductiveelimination of R¹ and R² gives the coupling product (R¹-R²) (Scheme 1,path A). If the reductive elimination of R¹ and R² is slow, Pd(R²)₂ canbe generated and Pd—R¹ can be transmetallated again with another R²—M(double transmetallation). Reductive elimination of Pd(R²)₂ leads to ahomocoupling product (Scheme 1, path B). It is believed that there is noreport of the intermediate (I), derived from oxidative addition of R¹Xto a Pd (0) species, undergoing double transmetallation with R²—M toform an intermediate (III). Although not completely understood, thesecond transmetallation, i.e., replacing the R¹ group with R² in theintermediate II, may be an aspect in a palladium-catalyzed homocouplingreaction. In this example, the target compound R² undergoes chemicalbond formation with itself by a homocoupling reaction.

[0028] Recently, considerable attention has been devoted to thepalladium enolate chemistry [Wang, Z.; Zhang, Z. Lu, X. Organometallics2000, 19, 775; Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999,121, 1473; Åhman, J.; Wolfe, J. P.; Troutman, M. V.; Palucki, M.;Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 1918; Sodeoka, M.;Shibasaki, M. Pure Appl. Chem. 1998, 70, 411 ] Several palladium enolatecomplexes have been well-characterized.

[0029] It is believed that the first transmetallation of an organoboronreagent to a palladium enolate was not reported or recognizedpreviously. Through investigation and experimentation, it wasdemonstrated that an enolate anion can serve as a leaving group similarto a bromide or iodide in a transmetallation process. Since oxidativeaddition of readily available a-bromocarbonyl compounds to a palladium(0) species can also readily occur, double transmetallation can becarried out. This double transmetallation reaction is depicted below.Here, an alpha-bromo phenyl carbonyl compound give a Pd(II)Br(enolate)intermediate (I), double transmetallation with aryl boronic acids yieldsan intermediate(III), which leads to a homocoupling product throughreductive elimination.

[0030] As an example of this type of intramolecular bond formation,methyl α-bromophenyl acetate ester 1 (1.0 mmol) and 3,5-dimethyl phenylboronic acid 2 (1.2 mmol) were used as reagents for Pd-catalyzedhomocoupling reactions. With these reagents, the homocoupling product 4was obtained in 70% yield exclusively under conditions withPd₂(dba)₃.CHCl₃ (0.025 mmol), rac-BINAP (0.05 mmol) and Cs₂CO₃ (1.5mmol) in dioxane (5 mL). When KF was used to replace Cs₂CO₃, an improvedyield of the homocoupling product (97%) was obtained. With an α-bromoketone 5, 6 and a homocoupling product 4 were obtained (Scheme 2).

[0031] To explore the scope of this reaction, the examination of severalaryl boronic substrates and other α-bromo carbonyl compounds wereinvestigated (Table 1). Using ethyl α-bromo acetate ester 7, bothhomocoupling and crosscoupling products were observed (Table 1, entries1, 3-5, 7, 9 and 12). Interestingly, substitution at the α-position ofα-bromo carbonyl compounds (e.g., 1) promotes the homocoupling reactionand inhibits the crosscoupling reaction (Table 1, entries 3 and 5).Furthermore, addition of water influences the selectivity betweenhomocoupling and crosscoupling products in this system. For example, inthe presence of water, the ratio of homocoupling and crosscouplingproduct switched from 30:70 to 70:30 in the coupling reaction ofortho-methyl phenyl boronic acid and ethyl α-bromide acetate ester(Table 1, entries 3 and 4). When the reaction was carried out using anα-substituted bromocarbonyl compound in the presence of water, onlyhomocoupling products were observed for many substrates, i.e., targetcompounds (Table 1, entries 2, 6, 8, and 10-17). It is noteworthy thatthis novel homocoupling coupling reaction appears to tolerate a varietyof functional groups, e g., aldehyde, methoxy, nitro groups, etc. Thepresence of an ortho-methoxyl group in aryl boronic acids also gave highyields of the homocoupling product (see, e.g., different selectivitiesin entries 3, 12 and 14). TABLE 1 Palladium-catalyzed Coupling Reactionof Aryl Boronic Acids^(a)

products^(b) entry subtrates solvent yields (%) Homo Cross 1 2a 7dioxane 89 50 50 2 2a 1 dioxane/H₂O 95 100 0 3 2b 7 dioxane 82 30 70 42b 7 dioxane/H₂O 89 70 30 5 2b 1 dioxane 88 94 6 6 2b 1 dioxane/H₂O 85100 0 7 2c 7 dioxane 92 50 50 8 2c 1 dioxane/H₂O 91 100 0 9 2d 7 dioxane92 50 50 10 2d 1 dioxane/H₂O 94 100 0 11 2e 1 dioxane/H₂O 93 100 0 12 2f7 dioxane 94 60 40 13 2f 1 dioxane/H₂O 92 100 0 14 2g 7 dioxane 89 100 015 2g 1 dioxane/H₂O 95 100 0 16 2h 1 dioxane/H₂O 89 100 0 17 2i 1dioxane/H₂O 90 100 0 ^(a)All reactions were performed using 1 mol %PdCl₂(rac-BINAP) and 300 mol % KF. The reactions were done at 100° C.for 2-24 h and progress of the reaction was monitored by TLC.^(b)Isolated yields were reported, and the ratio of homocoupling productvs crosscoupling product was determined by NMR.

[0032] To explain the experimental results, possible reaction mechanismsare illustrated in Scheme 3. In the first step, the reaction isinitiated by oxidative addition of an α-bromocarbonyl compound to aPd(0) species to form compound 8. Intermediate 9 is formed after thefirst transmetallation and isomerization of 9 generates a palladiumenolate intermediate 10, which undergoes a second transmetallation toyield the intermediate 12. Reductive elimination of 12 produces thehomocoupling product 4. On the other hand, the reductive elimination of9 gives the crosscoupling product 3. It is believed that isomerizationof 9 to 10 and transmetallation of 10 with the aryl boronic acid 2 arereversible. The homocoupling path (Sp²-Sp² coupling) is preferred whenreductive elimination of 9 is inhibited using an a-substitutedbromocarbonyl compound as a reagent (reductive elimination barrier ofSp²-Sp³ coupling is increased in the presence of a bulky Sp³ group). Inaddition, presence of water will hydrolyse 11 and drive the reactiontoward the intermediate 12. As the result, the homocoupling reaction ispromoted.

[0033] By employing a similar approach, homocoupling of many acetylenesunder the mild conditions can be achieved. The transformation isillustrated below. The mild condition and high yield of this Sp—Spcoupling is suitable to from polymers and oligomers. The reaction cantolerate a variety of functional groups. An advantage is that thereaction can be carried out under an inert atmosphere, as opposed to anoxidative environment.

[0034] For example, it is expected that HC≡CH may polymerize to formSp-carbon polymers, which can be converted as an useful material for itsconducting properties. Since high molecular weight polymer has not beprepared, this materials may have unexpected properties. Using YC≡CH asthe stopping agent, an oligomer such as YC≡C(C≡CC≡C)nC≡CY orYC≡C(C≡C)mC≡CY can be formed in the condensation polymerization. The Ycapping group can be SiMe3, COOR, CN, aryl, substituted aryl, alkyl andsubstituted alkyl. Another possibility is to make HC≡CZC≡CH first, whereZ is a bridge species. The bridge can be an aryl, substituted aryl,alkyl, substituted alkyl, heteroaryl species. Polymerization of thismonomer will lead to interesting materials. Where this description isonly outlined few chances of application of this new reaction, thepotential application is broad for making materials for mayapplications. The art of modem acetyline chemistry will teach thepractice of this chemistry in many key transformations [Diederich, F.;Stang, P. J. Metal-catalyzed Cross-coupling Reaction, Wiley-VCH, 1998].

[0035] Among the more challenging problems of metal-catalyzed couplingis the Sp3-Sp3 coupling reactions (both intramolecular andintermolecular cases). Especially, the reaction has to tolerate beta Hin both ends. By practicing an embodiment of the invention, coupling ofa variety of alkynes has been achieved leading to the possibility of avariety of new polyalkynes. Especially, hydroboration of alkenes with9-BBN or HB(OR)2 or asymmetric hydroboration of bis-alkenes willgenerate bis boron species. Coupling of these bis boron species can leadto formation up to four chiral centers. This strategy is very powerfulfor making many biologically active compounds. The hydroboration andcoupling reaction is a significant method for forming a ring structure.

[0036] While the examples provided above relate to forming C—C bonds, itis conceivable that C-heteroatom bond forming reaction and someoxidation reaction can be performed using an alpha halo carbonylcompound as the oxidate. Because that metal-enolate and metal-halide hasa different ability to do transmetallation and other transformation, weenvision that several new reactions are possible.

EXPERIMENTAL

[0037] General Procedures: All reactions and manipulations wereperformed in a nitrogen-filled glovebox or using standard Schlenktechniques. Column chromatography was performed using EM silica gel 60(230-400 mesh). ¹H NMR were recorded on Bruker WP-200, DPX-300, andAMX-360 and DRX-400 spectrometers. Chemical shifts were reported in ppmdown field from tetramethylsilane with the solvent resonance used as theinternal standard.

[0038] Materials: Aryl boronic acids and α-bromocarbonyl compounds werepurchased from Aldrich and were used directly without furtherpurification. Dioxane was dried and distilled from sodium/benzophenoneketyl under nitrogen and was stored in a sure-sealed bottle.

A General Procedure for the Pd-catalyzed Homo-Coupling Reaction of ArylBoronic Acids

[0039] PdCl₂(rac-BINAP) (0.01 mmol), KF (3.0 mmol) and an aryl boronicacid (1 mmol) were added in a dried Schlenk tube. The mixture was purgedwith nitrogen, and solvents [dioxane (5 mL) or dioxane (4 mL) and H₂0 (1mL)] were added. Under nitrogen, an α-bromo carbonyl compound [ethylbromoacetate ester (0.6 mmol) or methyl α-bromophenylacetate ester (0.6mmol)] was added and then the reaction mixture was stirred at 100 ° C.for 24 hours (h). After the reaction was completed, 5 mL of ethylacetate and ca. 3-5 g of silica gel were added to the reaction mixture.The solvent was removed under vacuum and the solid mixture was loaded ona silica gel column to remove the Pd catalyst. The following compoundsare known and references are provided:

sp²-sp² data (Biaryl) 1,1′-Diphenic acid diethyl ester

[0040] Steliou, Kosta; Salama, Paul; Yu, Xiaoping; JACSAT; J.Amer.Chem.Soc.; EN; 114; 4; 1992; 1456-1462; Sheley; Patterson; ORMSBG;Org.Mass Spectrom.; 9; 1974; 731,736; ¹H NMR (360 MHz, CDCl₃) δ 7.99(dd, J =1.4, 7.8, 2H), 7.50-7.48 (m, 2H), 7.41 (dt, J=1.3, 7.7, 2H),7.18 (dd, J=1.0, 7.6, 2H), 4.01 (q, J=7.2, 4H), 0.96 (t, J=7.2, 6H).

1,1′-Diphenonitrile

[0041] Hassan, Jwanro; Penalva, Vincent; Lavenot, Laurence; Gozzi,Christel; Lemaire, Marc; TETRAB; Tetrahedron; EN; 54; 45; 1998; 13793 -13804; ¹H NMR (360 MHz, CDCl₃) δ 7.80 (d, J=7.5, 2H), 7.70 (dd, J=7.7,7.5, 2H), 7.57-7.53 (m, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 139.76, 131.74,131.08, 128.75, 127.41, 115.77, 110.54.

2,2′-Dimethyl-biphenyl

[0042]¹H NMR (360 MHz, CDCl₃) 7.35-7.26 (m, 6H), 7.14 (dJ,=7.8, 2H),2.12 (s, 6H).

2,2′-Dimethoxy-biphenyl

[0043]¹H NMR (360 MHz, CDCl₃) 7.34 (dddJ,=1.8, 7.9, 7.8, 2H), 7.27 (dd,J=1.8, 7.9, 2H), 7.05-6.97 (m, 4H), 3.78 (s, 6H).

4,4′-Dimethyl-biphenyl

[0044]¹H NMR (300 MHz, CDCl₃) 7.62 (d,J=8.1, 4H), 7.37 (d,J=8.1, 4H),2.53 (s, 6H).

4,4′-Dimethoxy-biphenyl

[0045]¹H NMR (300 MHz, CDCl₃) 7.35 (d,J=8.5, 4H), 6.84 (d, J=8.5, 4H),3.71 (s, 6H).

Biphenyl-2,2′-Dicarbaldehyde

[0046]¹H NMR (360 MHz, CDCl₃) 9.79 (s, 2H), 8.01 (dd,J=1.1, 7.7, 2H),7.60(ddd,J=1.1, 7.5, 7.6, 2H), 7.54(dd,J=7.7, 7.6, 2H),7.45(d,J=7.5,2H).

3,3′-Dinitro-biphenyl

[0047]¹H NMR (360 MHz, CDCl₃) 8.43 (tJ=2.0, 2H), 8.23 (d, J=8.0, 2H),7.90 (d, J=8.0, 2H), 7.64 (t, J=8.0, 2H).

3, 5, 3′, 5′-Tetramethyl-biphenyl

[0048]¹H NMR (360 MHz, CDCl₃) 7.54 (s, 4H), 7.31 (s, 2H), 2.71 (s, 12H).

[1, 1′]Binaphthalenyl

[0049]¹H NMR (360 MHz, CDCl₃) 7.96-7.93 (m, 4H), 7.59 (t,J=8.1, 2H),7.55-7.45 (m, 4H), 7.40(d, J=8.2, 2H), 7.28 (t, J=8.2, 2H).

Biphenyl

[0050]¹H NMR (360 MHz, CDCl₃) 7.74 (d,J=7.8, 4H), 7.58 (dt, J=1.1, 7.5,4H), 7.49( tt, J=1.1, 7.4, 2H).

Indan-1-One

[0051]¹H NMR (400 MHz, CDCl₃) 7.72 (d,J=7.7, 1H), 7.55 (dd, J=7.7, 7.8,1H), 7.45 (d, J=7.6, 1H), 7.36 (dd, J=7.6, 7.8, 1H), 3.13-3.09 (m, 2H),2.67-2.64 (m, 2H).

Sp3-Sp3 coupling data 2,5-Dimethyl-2,5-diphenyl-hexanel ,1′-(1,1,4,4-tetramethyl-1,4-butanediyl)bis-benzene

[0052] Whitesides,G. M. et al.; JACSAT; J.Amer.Chem.Soc.; EN; 94; 1;1972; 232-239; Richards,D. H.; Scilly,N. F.; JSOOAX; J.Chem.Soc.C; EN;1969; 55-56.

2-Methyl-2-phenyl-propyl bromide

[0053] Tamao, Kohei; Yoshida, Jun-ichi; Akita, Munetaka; Sugihara,Yoshihiro; Iwahara, Takahisa; Kumada, Makoto; BCSJA8;Bull.Chem.Soc.Jpn.; EN; 55; 1; 1982; 255-260; ¹H NMR (300 MHz, CDCl₃) δ7.30-7.22 (m, 6H), 7.18-7.13 (m, 4H), 3.49 (s, 4H), 1.38 (s, 12H ); ¹³CNMR (75MHz, CDCl₃) δ 146.38, 128.64, 128.45, 127.05, 126.35, 126.12,47.33, 39.56, 29.42.

2,5-Dimethyl-2,5-diphenyl-hexane

[0054] Whitesides,G. M. et al.; JACSAT; J.Amer.Chem.Soc.; EN; 94; 1;1972; 232-239; ¹H NMR (300 MHz, CDCl₃) δ 7.31-7.28 (m, 4H), 7.21-7.19(m, 6H), 1.38 (s, 4H), 1.23 (s, 12H ); ¹³C NMR (75 MHz, CDCl₃) δ 149.71,128.39, 126.32, 125.73, 39.28, 37.86, 29.52.

2-Methyl-2-phenyl-propan-1-ol

[0055] Balzer, Hartmut H.; Berger, Stefan; MRCHEG; Magn.Reson.Chem.; EN;28; 5; 1990; 437-442; Ref. 1 5604628; Journal; Tamao, K.; Kakui, T.;Akita, M.; Iwahara, T.; Kanatani, R.; et al.; TETRAB; Tetrahedron; EN;39; 6; 1983; 983-990; R. S. et al.; JACSAT; J.Amer.Chem.Soc.; EN; 92;12; 1970; 3722-3729; ¹H NMR (360 MHz, CDCl₃) δ 7.32-7.26 (m, 3H),7.18-7.11 (m, 2H), 3.52 (s, 2H), 1.25 (s, 6H ); ¹³C NMR (75 MHz, CDCl₃)δ 146.76, 129.14, 128.86, 128.62, 126.68, 126.63, 73.51, 40.51, 25.75

Phenylethanol

[0056] Journal; Aitken, R. Alan; Armstrong, Jill M.; Drysdale, MartinJ.; Ross, Fiona C.; Ryan, Bruce M.; J.Chem.Soc.Perkin Trans.1; EN; 5;1999; 593-604; Ref. 1 5570193; Journal; Flippin, Lee A.; Gallagher,David W.; Jalali-Araghi, Keyvan; JOCEAH; J.Org.Chem.; EN; 54; 6; 1989;1430-1432; Ref. 1 5571848; Journal; Barluenga, Jose; Alonso-Cires,Luisa; Campos, Pedro J.; Asensio, Gregorio; SYNTBF; Synthesis; EN; 1;1983; 53-55; ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.27 (m, 5H), 4.66 (s, 2H),2.30 (br, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 140.96, 128.98, 128.14,127.50, 65.82; ¹H NMR (400 MHz, CDCl₃) δ 7.30 (d, J=8.5, 2H), 7.26 (d,J=8.5, 2H), 4.63 (s, 2H), 1.89 (br, 1H); ¹³C NMR (100 MHz, CDCl₃) δ139.65, 133.73, 129.07, 128.67, 64.91; Journal; Khotinsky; Melamed;CHBEAM; Chem.Ber.; 42; 1909; 3094; ¹H NMR (400 MHz, CDCl₃) δ 7.27-7.08(m, 7H), 2.83 (s, 2H)

2,2′-Dichloro-bibenzyl

[0057] Warren, Stuart; Wyatt, Paul; JCPRB4; J.Chem.Soc.Perkin Trans.1;EN; 2; 1998; 249-256; Tashiro,M. et al.; JOCEAH; J.Org.Chem.; EN; 43;1978; 1413-1419; ¹H NMR (360 MHz, CDCl₃) δ 7.38-7.32 (m, 2H), 7.18-7.11(m, 6H), 2.95 (s, 4H); ¹³C NMR (360 MHz, CDCl₃) δ 139.37, 134.43,131.02, 129.89, 127.96, 127.17, 34.21.

1,2-bis-(2-bromo-phenyl)-ethane

[0058] Kelly, T. Ross; Li, Qun; Bhushan, Vidya; TELEAY; TetrahedronLett.; EN; 31; 2; 1990; 161-164; Yamato, Takehiko; Sakaue, Naozumi;Komine, Masayasu; Nagano, Yoshiaki; JRMPDM; J.Chem.Res.Miniprint; EN; 7;1997; 1708-1735; ¹H NMR (360 MHz, CDCl₃) δ 7.71 (d, J=8.0Hz, 2H),7.40-7.34 (m, 4H), 7.25-7.71 (m, 2H), 3.21 (s, 4H); ¹³C NMR (360 MHz,CDCl₃) δ 141.01, 133.30, 131.05, 127.87, 124.92, 36.87.

1-Bromo-6-choro-hexane

[0059]¹H NMR (400 MHz, CDCl₃) δ 3.52 (t, J=6.6 Hz, 2H), 3.40 (t, J=6.7Hz, 2H), 1.87-1.80( m, 2H), 1.79-1.75( m, 2H), 1.47-1.41( m, 4H); ¹³CNMR (75 MHz, CDCl₃) δ 45.30, 34.08, 32.94, 32.75, 27.82, 26.43.

1,12-dicholo-dodecane

[0060] Turro, Nicholas J.; Han, Nianhe; Lei, Xue-gong; Fehlner, JamesR.; Abrams, Lloyd; JACSAT; J.Amer.Chem.Soc.; EN; 117; 17; 1995;4881-4893; ¹H NMR (300 MHz, CDCl₃) δ 3.51 (t, J=6.8 Hz, 4H),7.271.79-1.70 (m, 4H), 1.42-1.38 (m, 4H), 1.26-1.23 (m, 12H); ¹³C NMR(90MHz, CDC1₃) δ 45.56, 33.04, 29.86, 29.26, 27.26.

Hexadecane

[0061] Chatgilialoglu, C.; Guerrini, A.; Lucarini, M.; JOCEAH;J.Org.Chem.; EN; 57; 12; 1992; 3405-3409; ¹H NMR (400 MHz, CDCl₃) δ1.30- 1.19 (m, 26H), 0.86 (t, J=6.8Hz, 6H); ¹³C NMR (100 MHz, CDCl₃) δ32.33, 30.10, 30.06, 29.77, 23.10.

Tetradecanedinitrile

[0062] Saotome,K. et al.; BCSJA8; Bull.Chem.Soc.Jpn.; EN; 39; 1966;480-484;

6-bromo-hexanoic acid ethyl ester

[0063] McHintosh, John M.; Pillon, Lilianna Z.; Acquaah, Samuel O.;Green, James R.; White, Graham S.; CJCHAG; Can.J.Chem.; EN; 61; 1983;2016-2021;

[0064] Somekawa, Kenichi; Okuhira, Hiroyuki; Sendayama, Masayuki;Suishu, Takaaki; Shimo, Tetsuro; JOCEAH; J.Org.Chem.; EN; 57; 21; 1992;5708-5712; ¹H NMR (300 MHz, CDCl₃) δ 4.03 (q, J=7.2, 2H), 3.23 (t,J=6.8, 2H), 2.18 (t, J=7.3, 2H), 1.76-1.71 (m, 2H), 1.55-1.48 (m, 2H),1.36-1.31( m, 2H), 1.13 (t, J =7.2, 3H); ¹³C NMR (75 MHz, CDCl₃) δ173.81, 60.67, 34.47, 33.96, 32.80, 28.03, 24.50, 14.69.

Dodecanedioic acid diethyl ester

[0065] Menger, F. M.; Wood, M. G.; Richardson, S.; Zhou, Q.; Elrington,A. R.; Sherrod, M. J.; JACSAT; J.Amer.Chem.Soc.; EN; 110; 20; 1988;6797-6803; ¹H NMR (400 MHz, CDCl₃) δ 4.04 (q, J=7.2, 4H), 2.21( t,J=7.4, 4H), 1.58-1.50 (m, 4H), 1.24-1.16 (m, 18H)

1,2-Diphenyl-ethane

[0066] Hartman, Stephen J.; Kelusky, Eric C.; CJCHAG; Can.J.Chem.; EN;60; 1982; 2654-2660; Marquet, Jorge; Moreno-Manas, Marcial; Pacheco,Pedro; Prat, Maria; Katritzky, Alan R.; Brycki, Bogumil; TETRAB;Tetrahedron; EN; 46; 15; 1990; 5333-5346; ¹H NMR (400 MHz, CDCl₃)δ7.30-7.26 (m, 4H), 7.21-7.18 (m, 6H), 2.92 (s, 4H); ¹³ C NMR (100 MHz,CDCl₃) δ 142.19, 128.86, 128.75, 126.33, 38.37.

2,3-Diphenyl-butane

[0067] Kim, Seung-Hoi; Rieke, Reuben D.; JOCEAH; J.Org.Chem.; EN; 65; 8;2000; 2322 - 2330; ¹H NMR (400 MHz, CDCl₃) δ 7.25-7.21 (m, 2H),7.15-7.13 (m, 3H), 7.10-7.06 (m, 2H), 7.02-7.00( m, 1H), 6.94-6.92( m,2H), 2.88-2.84 (m, 1.2H), 2.73-2.71 (m, 0.8H), 1.20 (dd, J=1.8, 5.0,3.6H), 0.95 ( dd, J=2.0, 4.8, 2.4H ); ¹³C NMR (100 MHz, CDCl₃) δ 146.91,146.26, 128.71, 128.25, 128.20, 128.04, 126.48, 126.12, 47.69, 46.90,21.47, 18.37.

1,2-diphenyl-ethanone

[0068] Journal; Kawatsura, Motoi; Hartwig, John F.; JACSAT; J. Amer.Chem. Soc.; EN; 121; 7; 1999; 1473 - 1478; ¹H NMR (360 MHz, CDCl₃) 67.93 (d, J=7.7, 2H), 7.48 (td, J=1.2, 7.3, 1H), 7.37 (dd, J=7.3, 7.7,2H), 7.26-7.23 (m, 2H), 7.20-7.15( m, 3H), 4.20 (s, 2H); ¹³C NMR (100MHz, CDCl₃) δ 198.04, 137.00, 134.95, 133.59, 129.89, 129.09, 129.06,129.03, 127.31, 45.91.

sp²-sp² data (vinyl-vinyl) data 1,4-Diphenyl-buta-1,3-diene

[0069] Nishihara, Yasushi; Ikegashira, Kazutaka; Toriyama, Fumihiko;Mori, Atsunori; Hiyama, Tamejiro; BCSJA8; Bull.Chem.Soc.Jpn.; EN; 73; 4;2000; 985-990; ¹H NMR (400 MHz, CDCl₃) δ 7.48 (d, J=7.5 Hz, 4 H), 7.38(dd, J=7.5, 7.0, 4H), 7.28 (t, J=7.0, 1H), 6.95 (dd, J=14.7, 2.7 Hz, 2H), 6.71 (dd, J=14.7Hz, 2.7H); ¹³C NMR (90 MHz, CDCl₃) δ 135.35, 130.83,127.25, 126.67, 125.57, 124.40.

sp-sp Coupling data Diphenylbutadiyne

[0070] Aitken, R. Alan; Herion, Hugues; Horsburgh, Caroline E. R.;Karodia, Nazira; Seth, Shirley; JCPRB4; J.Chem.Soc.Perkin Trans.1; EN;5; 1996; 485-490; ¹H NMR (400 MHz, CDCl₃) δ7.55-7.50 (m, 4H), 7.37-7.32(m, 6H)

2,7-Dimethyl-octa-3,5-diyne-2,7-diol

[0071] Raj, C. Paul; Braverman, S.; SYNCAV; Synth.Commun.; EN; 29; 15;1999; 2629-2638; ¹H NMR (400 MHz, CD₂Cl₂) δ 2.02 (s, 2H), 1.42 (s, 12H);¹³C NMR (100 MHz, CD₂Cl₂) δ 84.92, 66.65, 66.17, 31.64; ¹H NMR (400 MHz,CDCl₃)δ 7.55-7.50 (m, 4H), 7.37-7.32 (m, 6H).

Bis-(4-ethyl-phenyl)-butadiyne

[0072] Uchida,A. et al.; JOCEAH; J.Org.Chem.; EN; 37; 23; 1972;3749-3750; ¹H NMR (360 MHz, CDCl₃)δ 7.43 (d, J=8.1, 4H), 7.15 (d, J=8.1,4H), 2.67( q, J 7.6, 4H), 1.25( t, J=7.6, 6H); ¹³C NMR (90 MHz, CDCl₃) δ146.1, 132.9, 128.4, 119.5, 82.0, 73.9, 29.3, 15.6.

4,4′-Di-n-propyldiphenyldiacetylene

[0073]¹H NMR (360 MHz, CDCl₃) δ 7.36 (d, J=8.2, 4H), 7.02(d, J=8.2, 4H),2.52(t, J=7.6, 4H), 1.78-1.54(m, 4H), 0.91(t, J=7.3, 6H); ¹³C NMR (90MHz, CDCl₃) δ 142.0, 132.7, 131.6, 130.6, 119.7, 62.7, 37.8, 24.8, 14.4.

Di-cyclohexy-1-enyl-butadiyne

[0074]¹H NMR ( 300 MHz, CDCl₃) δ 6.23-6.21(m, 2H ), 2.10-2.09 (m, 8H ),1.61-1.55(m, 8H); ¹³C NMR (75 MHz, CDCl₃) δ 138.5, 120.3, 83.0, 71.9,29.1, 26.3, 22.5, 21.7.

Hexadeca-7,9-diyne

[0075]¹H NMR ( 360 MHz, CDC1₃) δ 2.22 (t, J=6.8 MHz, 4H), 1.53-1.47 (m,4H), 1.40-1.20 (m, 12H), 0.87 (t, J=6.6, 6H); ¹³C NMR ( 90 MHz, CDCl₃) δ77.9, 65.7, 31.7, 28.9, 28.7, 22.9, 19.6, 14.4.

Dodeca-5,7-diyne-1,12-diol

[0076]¹H NMR ( 360MHz, CDCl₃) δ 3.65( t, J=6.2, 4H), 2.28( t, J=6.5,4H), 1.70-1.57 (m, 8H), 1.34 (br, 2H); ¹³C NMR ( 90MHz, CDCl₃) δ 77.6,66.0, 62.7, 32.1,25.0,19.4.

1,4-Bis(1-hydroxycyclohexyl) buta-1,3-diyne

[0077] TETRAB; Tetrahedron; EN; 34; 1978; 1323-1332; ¹H NMR (CDCl₃) δ1.98 (br, 2H), 1.92-1.88 (m, 4H), 1.74-1.66 (m, 4H), 1.61-1.48 (m, 8H),1.28-1.21 (m, 4H); ¹³C NMR (CDCl₃) δ 83.4, 69.6, 68.7, 40.1, 25.4, 23.5.

1,1′-butadiynediyl-bis-cyclopentanol

[0078]¹H NMR (360 MHz, CDCl₃) δ 2.02-1.92 (m, 8H), 1.87-1.67 (m, 8H),1.20 (br, 2H), ¹³C NMR ( 90 MHz, CDCl₃) δ 82.2, 73.7, 66.3, 41.3, 22.3.

1,8-diphenyl-octa-3,5-diyne

[0079]¹H NMR ( 360 MHz, CDCl₃) δ 7.25-7.11 (m, 10H ), 2.76 (t, J=7.4,4H), 2.46 (t, J=7.5, 4H); ¹³C NMR (90 MHz, CDCl₃) δ 140.6, 128.9, 128.8,126.8, 77.3, 66.3, 35.3, 21.9.

2,7-dimethyl-octa-3,5-diyne-2,7-diol

[0080] Raj, C. Paul; Braverman, S.; SYNCAV; Synth.Commun.; EN; 29; 15;1999; 2629-2638; ¹H NMR (400 MHz, CD₂Cl₂) δ 2.02 (s, 2H), 1.42 (s, 12H);¹³C NMR (100 MHz, CD₂Cl₂) δ 84.92, 66.65, 66.17, 31.64.

Tetracosa-1 1,13-diyne

[0081]¹H NMR ( 360 MHz, CDCl₃) δ 2.22 (t, J=6.6, 4H), 1.54-1.45 (m, 4H),1.37-1.24 (m, 28H), 0.86 (t, J=6.7, 6H); ¹³C NMR ( 90MHz, CDCl₃) δ 77.2,64.9, 31.5, 29.2, 29.1, 28.9, 28.7, 28.5, 28.0, 22.3, 18.8, 13.7.

Deca-4,6-diynedinitrile

[0082]¹H NMR ( 360 MHz, CDCl₃) δ 2.64(t, J=6.4, 4H), 2.57(t, J=6.4, 4H);¹³C NMR ( 90 MHz, CDCl₃) δ 118.0, 74.3, 67.8, 17.5, 17.0.

Dichloro- deca-4,6-diyne

[0083]¹H NMR (CDCl₃) δ 3.64 (t, J=6.2, 4H), 2.46 (t, J=6.8, 4H),2.05-1.94 (m, 4H); ¹³C NMR (CDCl₃) δ 76.2, 66.5, 43.8, 31.5, 17.7.

Polymerization of alkynes

[0084] A wide variety of alkynes can be made by combining a alkyne witha catalysts and an alpha-halo carbonyl. These alkynes can be polymerizedalone or with an end-capping agent. In an embodiment of the presentinvention, one or more bonds is formed between one of more alkynes toform an oligomer or polymer. For example, the polymer can have thefollowing structure:

Q-linker-(R^(a)C≡C)n-linker-( R^(a)C≡C—C≡C)m-linker-Q

QC≡C(C≡CC≡C)nC≡CQ

QC≡C(C≡C)mC≡CQ

[0085] or

QC≡C(C≡C-linker-C≡C)nC≡CQ

[0086] wherein: R^(a) is a substituted or unsubstituted diradical of analkane, alkene, alkyne, if present; Q is H, a metal, an organometallicspecies, or a substituted or unsubstituted silane, SiMe₃, COOR′, aryl,alkyl, siloxane, CN, or, CONHR′; where R′ is an alkyl or aryl group;linker is a joining bond, i.e. the linker denotes a bond between the twogroups. Linker also represents a substituted or unsubstituted diradicalof an alkane, alkene, alkyne, aryl, arylene, aromatic, or siloxane.These polymers can be of a high molecular weight, e.g. where n or m hasa value as high millions. In one aspect, the values of n or m is from 1to 100,000, e.g., n or m is from 1 to 1,000. In another aspect polymericmaterials of where n and/or m is 10 to 100 can be formed. An example ofa polyacetylene end-capped with phenylacetylene is provided below.

[0087] A mixture of Acetylene ( 194 mg, 1 mmol), Cul ( 9.5 mg, 0.05mmol), PdCl₂(BINAP) ( 40 mg, 0.05 mmol), Desyl chloride ( 138.4 mg, 0.6mmol) and DABCO ( 134.4 mg, 1.2 mmol) in 5 ml THF was stirred at roomtemperature. To this solution, a small amount of Phenyl acetylene ( 10.4mg, 0.1 mmol) was added and the reaction mixture was stirred for 2 days.The solvent was removed in vacuo and 10 ml. of MeOH was added to theresidue. The solid was filtered and washed a few times with methanol.After drying, a brownish black solid was obtained.

[0088] The following table illustrates the polymerization of a widevariety of alkynes by the above approach. It is understood that thepolymeric products are produced from the corresponding alkyne. Forexample, the polymer of entry 1 is produced from the 1,7-dioctyne. Therepeating unit is indicated by the subscript “n”. Polymer YieldCharacterization¹ 1

51% GPC - 994 color - Brownish yellow solid 2

55% solid state NMR - 137, 129, 78.8, 68.7, 28.9, 19.7; GPC - 1194color - Same as above 3

45% U.V.-Vis - 420(max), 316, 332 NRM - 0.6, 0.83, 0.97, 1.23, 1.35,1.52, 1.79, 2.15, 3.96, 6.95 GPC - 4575 Color - Orange/red 4

— U.V.-Vis - 204(Max), 638, 650 I.R. - 3054, 2150, 1597, 696 ¹³C NMRsolid - 112 GPC - 2321 color - Black color - Black 5

—

U.V.-Vis - 244 color - Brown 6

—

[0089] Only the preferred embodiment of the present invention andexamples of versatility are shown and described in the presentdisclosure. It is to be rstood that the present invention is capable ofuse in various other binations and environments and is capable ofchanges or modifications within scope of the inventive concept asexpressed herein.

What is claimed is:
 1. A method of forming a chemical bond, the methodcomprising: combining at least one α-halo carbonyl compound with atleast one transmetallation reagent comprising a target compound; andforming a chemical bond to or within the target compound.
 2. The methodof claim 1, comprising forming the a chemical bond to or within thetarget compound in the presence of a catalysts selected from the groupconsisting of Pd(0), Ni(0), Rh(I), Pt(0), Ir(0), Cu(I), Mo(0), Mo(II),and Ru(II).
 3. The method of claim 1, wherein the transmetallationreagent contains one or more elements consisting of B, Sn, Al, Zn, Mg,Zr, Cu, Hg, and Si.
 4. The method of claim 1, wherein the a-halocarbonyl compound is a α-bromo carbonyl compound.
 5. The methodaccording to claim 1, comprising an alkyl or aryl boronic acid as thetarget compound undergoing chemical bond formation.
 6. The methodaccording to claim 1, comprising an alkyl or aryl Zn compound as thetarget compound and coupling the alkyl or aryl Zn compound as the bondforming step.
 7. The method according to claim 2, wherein thetransmetallation reagent comprises a boron derivative of ROH, RNH₂,RN(R′)H, RSH, and R2P(O)H.
 8. The method of claim 1, wherein thecatalysts is selected from the group consisting of PtCl₂; H₂PtCl₄;Pd₂(DBA)₃; Pd(OAc)₂; PdCl₂(RCN)₂; PdCl₂(diphosphine); [Pd(allyl)Cl]₂;Pd(PR₃)₄; [Rh(NBD)₂]X; [Rh (NBD)C]₂; [Rh(COD)Cl]₂; [Rh(COD)₂]X;Rh(acac)(CO)₂; Rh(ethylene)₂(acac); [Rh(ethylene)₂Cl]₂; RhCl(PPh₃)₃;Rh(CO)₂Cl₂; RuHX(L)₂; RUX₂(L)₂; Ru(arene)X₂(diphosphine); Ru(arylgroup)X₂; Ru(RCOO)₂(diphosphine); Ru(methallyl)2(diphosphine); Ru(arylgroup)X₂(PPh₃)₃; Ru(COD)(COT); Ru(COD)(COT)X; RuX₂(cymen); Ru(COD)_(n);Ru(aryl group)X₂(diphosphine); RuCl₂(COD); (Ru(COD)₂)X;RuX₂(diphosphine); RuCl₂(═CHR)(PR′₃)₂; Ru(ArH)Cl₂; Ru(COD)(methallyl)₂;(Ir (NBD)₂Cl)₂; (Ir(NBD)₂)X; (Ir(COD)₂Cl)₂; (Ir(COD)₂)X; CuX (NCCH₃)₄;Cu(OTf); Cu(OTf)₂; Cu(Ar)X; CuX; Ni(acac)₂; NiX₂; (Ni(allyl)X)₂;Ni(COD)₂; NiCl₂(diphosphine); MoO₂(acac)₂; wherein each R and R′ isindependently selected from the group consisting of: alkyl or aryl; Aris an aryl group; and X is I, Br, Cl, OTf, BF₄, SbF₆, BAr₄; and Lrepresents a ligand.
 9. The method of claim 8, wherein the diphosphineinclude dppe, dppp, dppb, dppf, rac-Binap, chiral bisphosphines, DuPhos,BINAP, BPPM, DIPAMP, DIOP, MCCPM, BCPM, BICP, PennPhos, BPE, ChiraPhos,NorPhos, Degphos, BPPFA, JosiPhos, TRAP, TolBINAP, H8-BINAP, BINAPO,MOP, BINAPHOS, BIPHEMP, SEGPHOS, TUNAPHOS, KetalPhos, f-KetalPhos,HydroPhos, f-HydroPhos, Binaphane, f-Binaphane, FAP; and the monophosphine includes: PPh₃, P(o-tolyl)₃, tri(2,6-dimethylphenyl)phosphine,P^(t)Bu₃, PCy₃, P(2-Furyl)₃ and PPh₂(o-ArC₆H₄).
 10. The method of claim1, further admixing a base selected from the group consisting of Et₃N,DABCO, Et₂NH, NaOR, Na₂CO₃, KF, K₃PO₄, NaOAc, KOH, and R^(b)NX, whereR^(b) is one or more alkyl groups and X is an anion.
 11. A process ofhydroboration and asymmetric hydroboration of boric compounds andcoupling of bisboronic compounds by either intramolecular orintermolecular coupling, the process comprising: combining at least oneα-halo carbonyl compound with at least one transmetallation reagentcomprising a boric compound; and coupling the boric compound.
 12. Themethod of claim 1, comprising forming one or more bonds between one ofmore alkynes.
 13. The method of claim 12, wherein the alkyne isacetylene.
 14. The method of claim 12, comprising polymerizing acetyleneor diacetylene.
 15. The method of claim 1, comprising forming one ormore bonds between one of more alkynes to form an oligomer or polymerhaving the following structure: QC≡C(C≡CC≡C)nC≡CQ or QC≡C(C≡C)mC≡CQorQC≡C(C≡C-linker-C≡C)nC≡CQ wherein: Q is H, a metal, an organometallicspecies, or a substituted or unsubstituted silane, SiMe₃, COOR′, aryl,alkyl, siloxane, CN, or, CONHR′; where R′ is an alkyl or aryl group;linker is a joining bond, a substituted or unsubstituted diradical of analkane, alkene, alkyne, aryl, arylene, aromatic, or siloxane; n is 1 to100000; and m is 1 to
 100000. 16. The method of claim 1, wherein thetransmetallation reagent comprises an alcohol as the target compound andforming a chemical bond within the target compound by oxidizing thealcohol to an aldehyde or ketone.
 17. The method of claim 16, oxidizingthe alcohol to an enone.
 18. A composition comprising at least one(x-halo carbonyl compound; and one or more transmetallation reagents.19. The composition of claim 18, fuirther comprising at least one base.20. The composition of claim 19, further comprising a catalyst.